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Issue 39, 2017
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Dynamics of π*-resonances in anionic clusters of para-toluquinone

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Frequency-resolved photoelectron spectroscopy applied to mass-selected cluster anions is an insightful approach to characterise the dynamics of π*-resonances with microsolvation. Here, the technique is demonstrated with monomer, dimer and trimer radical anions of para-toluquinone (pTQ) over a ∼1 eV excitation window above the detachment threshold. The pTQ spectra show similar resonances and dynamics to para-benzoquinone, a prototype electrophore. The dimer, (pTQ)2, has a π-stacked geometry and shows a competition between photodissociation and prompt autodetachment. The trimer, (pTQ)3, also has a π-stacked cluster geometry and shows vibrational autodetachment from a non-valence state up to ∼0.7 eV above-threshold, outcompeting dissociation. At higher photoexcitation energies, (pTQ)3 shows monomer-like dynamics, blue-shifted in photoexcitation energy by the cluster cohesion energy. Overall, the study highlights the variety of non-adiabatic dynamics available to π*-resonances and the profound changes that occur through clusterization with one and two monomers.

Graphical abstract: Dynamics of π*-resonances in anionic clusters of para-toluquinone

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Publication details

The article was received on 30 May 2017, accepted on 17 Sep 2017 and first published on 18 Sep 2017

Article type: Paper
DOI: 10.1039/C7CP03628K
Citation: Phys. Chem. Chem. Phys., 2017,19, 26589-26595

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    Dynamics of π*-resonances in anionic clusters of para-toluquinone

    J. N. Bull and J. R. R. Verlet, Phys. Chem. Chem. Phys., 2017, 19, 26589
    DOI: 10.1039/C7CP03628K

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